OXOSYNTHESIS, UDEX

AND FISCHER TROPSCH

SYNTHESIS
 UDEX PROCESS
• Ethylene glycol mixed with water forms solvent for aromatics.
o
• Aromatic rich stock heated to 150 C and 8-10 bars - sent to extractor (1), where
udder solution contacts aromatic rich stock

• Raffinate from top of extractor goes to water washer (3), where solvent is washed
off by spray of water.

• From the top, raffinate is obtained and by steaming, remaining solvent stains can be
removed.

• Extract from (1) goes to fractionator (2)-top product containing aromatics and small
amount of solvent -distilled in column (5) to get aromatics and solvent from the
bottom of (5) joins (1)

• Raffinate washings collected and fractionated in column (4) to drive off excess
water to maintain degree of dilution (80-90%).

• Solvent recycling is 5-6 times hydrocarbon feed.

• Ethylene glycol - suitable to extract light hydrocarbons, DMF, DMSO, liq. SO2 -
improves smoke point
OXO ALDEHYDES AND ALCOHOLS
(Hydroformylation Reaction)
• Hydroformylation of olefins (Oxo reaction) produces aldehydes
with one more carbon than the reacting olefin.

• Eg. when ethylene is used, propionaldehyde is produced.

• This reaction is especially important for the production of higher

aldehydes that are further hydrogenated to the corresponding
alcohols.

• The reaction is catalyzed with cobalt or rhodium complexes.

• Olefins with terminal double bonds are more reactive and

produce aldehydes which are hydrogenated to the
corresponding primary alcohols.
• With olefins other than ethylene, the
hydroformylation reaction mainly produces a
straight chain aldehyde with variable amounts of
branched chain aldehydes. The reaction could be
generally represented as:
• The largest commercial process is the
hydroformylation of propene, which yields n-
butyraldehyde and isobutyraldehyde.

• n-Butyraldehyde (n-butanal) is either hydrogenated

to n-butanol or transformed to 2- ethyl-hexanol via
aldol condensation and subsequent hydrogenation.

• 2- Ethylhexanol is an important plasticizer for

polyvinyl chloride.
• Other olefins applied in the hydroformylation
process with subsequent hydrogenation are
propylene trimer and tetramer for the production of
decyl and tridecyl alcohols, respectively, and C7
olefins (from copolymers of C3 and C4 olefins) for
isodecyl alcohol production.
• Some processes use a rhodium catalyst complex
incorporating phosphine ligands HRhCO(PPh3)2 at relatively
lower temperatures and pressures and produce less
branched aldehydes.

• Older processes use a cobalt carbonyl complex HCo(CO)4

at higher pressures and temperatures and produce a higher
ratio of the branched aldehydes.

• The hydroformylation reaction using phosphine ligands

occurs in an aqueous medium.

• A higher catalyst activity is anticipated in aqueous media

than in hydrocarbons.

• Selectivity is also higher. Having more than one phase allows

for complete separation of the catalyst and the products.
• In order to make the catalysts soluble in water, ionic ligands are attached to the catalyst.

• The Rhurchemie/Rhone-Poulenc process for the production of butyraldehyde from propylene

is based on this technology.

• Hydroformylation of higher olefins using ionic phosphine catalysts that are solubilized in both
reactants and products was investigated by Union Carbide researchers.

• This yields a one-phase homogeneous system. The catalyst is recovered outside the
reaction zone. Although this is a single-phase system, these catalysts could be induced to
separate into a nonpolar product and polar catalyst phases. This technology provides an
effective means of catalyst recovery.

• Cobalt catalysts have also been investigated. Hoechest researchers have developed a
water soluble cobalt cluster compound that can hydroformylate olefins in a two-phase
system.

• Hydroformylation of higher olefins is possible when polyethylene glycol is used as a solvent.

• Higher olefins have greater affinity for ethylene glycol than for water, therefore allowing
greater reaction rates.

• To facilitate the separation of the products, pentane is added to the system. The reaction
takes place at 120°C and 70 KPa. When 1-hexene is used, the ratio of n-heptanal to the iso-
was 0.73–3.75.
 Flow diagram of Ruhrchemie/
Rhone-Poulenc (RCH/RP) process.
 RCH/RP Process description
• The unit is essentially a continuously stirred tank reactor, followed by a phase separator
and strip column.

• The reaction takes place in the reactor (1) which contains the catalyst solution and the
reactor is fed with synthesis gas and propene.

• Before entering the reactor, the synthesis gas is first passed through a stripping column
(4) in countercurrent to the crude aldehyde stream in order to recover the unreacted
propene.

• The crude aldehyde product leaves the top of the reactor and passes into the decanter
(2) where it is degassed and separated from the entrained catalyst solution.

• The catalyst solution is returned to the reactor via heat exchanger (3).

• The organic phase, containing the raw aldehyde, then passes through stripping column
(4).

• Then the raw aldehyde is separated into n- and iso-butanal in distillation column (5).

• The heat of the reaction is used in a falling film evaporator (6) that has a function as
reboiler of this distillation column.
Wulff Process
 FISCHER-TROPSCH SYNTHESIS
• Liquid transportation hydrocarbon fuels and various other
chemical products can be produced from syngas via the
well-known and established catalytic chemical process
called Fischer-Tropsch (FT) synthesis, named after the
original German inventors, Franz Fischer and Hans
Tropsch in the 1920s.
• Depending on the source of the syngas, the technology is
often referred to as coal-to-liquids (CTL) and/or gas-to-
liquids (GTL).
• Examples of current operating CTL plants include Sasol's
Sasolburg I and II plant, and an example of a GTL FT
process is Shell's plant in Bintulu, Malaysia.
• Fixed bed, Fluidised bed or Slurry bed reactors
• The gasification island consists of all the supporting process technologies of
coal handling & feed preparation, heat recovery, syngas cleanup and
conditioning, water-gas-shift, sulfur recovery, etc.

• The clean syngas leaving the gasification island is sent onto the FT
synthesis island, where the clean shifted syngas is converted into primary
products of wax, hydrocarbon condensate, tail gas, and reaction water.

• The wax is sent on to an upgrading unit for hydrocracking in the presence of

hydrogen, where it is chemically split into smaller molecular weight
hydrocarbon liquids.

• A hydrogen recovery unit is used to extract the required quantity of

hydrogen from the tail gas as shown, or alternatively from the feed syngas
stream.

• The reaction products, along with that from the upgrading section, are
fractionated into the final products of diesel, naphtha, and other light ends,
depending on the desired product mix.

• The production facility is supported by several utility plants, including the

power train.
 Chemistry
• The Fischer-Tropsch process is a catalytic chemical reaction in which carbon monoxide (CO) and
hydrogen (H2) in the syngas are converted into hydrocarbons of various molecular weights
according to the following equation:
• (2n+1)H2 + nCO →CnH(2n+2) + nH2O
• Where n is an integer. Thus, for n=1, the reaction represents the formation of methane, which in
most CTL or GTL applications is considered an undesirable byproduct.
• The Fischer-Tropsch process conditions are usually chosen to maximize the formation of higher
molecular weight hydrocarbon liquid fuels which are higher value products.
• There are other side reactions taking place in the process, among which the water-gas-shift reaction
is predominant.
• CO+H2O→H2+ CO2
• Depending on the catalyst, temperature, and type of process employed, hydrocarbons ranging
from methane to higher molecular paraffins and olefins can be obtained.
• Small amounts of low molecular weight oxygenates (e.g., alcohol and organic acids) are also
formed.
• The Fischer-Tropsch synthesis reaction, in theory, is a condensation polymerization reaction of CO.
• Its products obey a well-defined molecular weight distribution according to a relationship known as
Shultz-Flory distribution.
 Catalysts
• Catalysts considered for Fischer-Tropsch synthesis are based on transition metals of iron, cobalt, nickel and
ruthenium.

• FT catalyst development has largely been focused on the preference for high molecular weight linear alkanes and
diesel fuels production.

• Among these catalysts, it is generally known that:

• Nickel (Ni) tends to promote methane formation, as in a methanation process; thus generally it is not desirable

• Iron (Fe) is relatively low cost and has a higher water-gas-shift activity, and is therefore more suitable for a lower
hydrogen/carbon monoxide ratio (H2/CO) syngas such as those derived from coal gasification

• Cobalt (Co) is more active, and generally preferred over ruthenium (Ru) because of the prohibitively high cost of
Ru

• In comparison to iron, Co has much less water-gas-shift activity, and is much more costly.

• Given these constraints, commercially available FT catalysts are either cobalt or iron based.

• In addition to the active metal, the Fe catalysts at least typically contain a number of promoters, including
potassium and copper, as well as high surface area binders/supports such as silica and/or alumina.

• Only iron-based FT catalysts are currently used commercially for converting coal-derived syngas into FT liquids,
given Fe catalyst's inherent water gas shift capability to increase the H2/CO ratio of coal-derived syngas, thereby
improving hydrocarbon product yields in the FT synthesis.

• Fe catalysts may be operated in both high-temperature regime (300-350°C) and low-temperature regime
(220-270°C), whereas Co catalysts are only used in the low-temperature range. This is a consequence of higher
temperatures causing more methane formation, which is worse for Co compared to Fe.
• Co catalysts are 230 times more expensive than Fe but are a useful alternative to Fe catalysts for FT
synthesis because they demonstrate activity at lower synthesis pressures, so higher catalyst costs
can be offset by lower operating costs. Also, coke deposition rate is lower for Co catalyst than Fe
catalyst; consequently, Co catalysts have longer lifetimes. Co catalysts have a long lifetime/greater
activity; i.e., Co catalysts are replaced less frequently.

• Although there are differences in the product distribution of Co and Fe catalysts at similar
temperatures and pressures (e.g. at 30 atm and 240°C a Co catalyst has somewhat higher selectivity
for heavier hydrocarbons than Fe would have) the product distribution is primarily driven by the
choice of operating temperature: high temperature results in gasoline/diesel ratio of 2:1; low
temperature results in gasoline/diesel 1:2 more or less no matter if the catalyst if Fe or Co.

• Higher temperatures shift selectivity towards lower carbon number products and more hydrogenated
products; branching increases and secondary products such as ketones and aromatics also
increase.

• If maximizing the gasoline product fraction, it is best to use an iron catalyst at a high temperature in a
fixed fluid bed reactor. If maximizing the diesel product fraction, a slurry reactor with a cobalt catalyst
is the best choice (see following discussion on reactor types).

• Both Fe and Co FT catalysts are sensitive to the presence of sulfur compounds in the syngas and
can be poisoned by them. However, the sensitivity of the catalyst to sulfur is higher for Co-based
catalysts than for their iron counterparts. This is one reason why Co catalysts are preferred for FT
synthesis with natural gas derived syngas, where the syngas has a higher H2:CO ratio and is
relatively lower in sulfur content; Fe catalysts are preferred for lower quality feedstocks such as coal.